Dimethylene quaternary ammonium salts



Patented May 12, 1942 UNITED, STATES PATENT OFFICE 1 DIMETHYLENE ofiif rimar AMMONIUM v SALTS Louis B. Bock, Glenside, Pa., assignor to Riihm &Haas Company, Philadelphia, Pa.

No Drawing.

Application March 30, 1940, Serial No. 327,079 7 7 Claims. (Cl. 260-404)This invention relates to quaternary ammonium compounds of the generalformula R--NH-CHzM CHzO R wherein R. is an aliphatic group, R1 is alsoan aliphatic group, X is a halogen, and R2 and R3 represent loweraliphatic groups when taken singly or, when taken together, represent adivalent aliphatic group which jointly with the nitrogen forms aheterocycle. These compounds are of marked reactivity, under properconditions, toward such materials as starch,-cellulose ethers, polyvinylalcohol, cellulose, regenerated cellulose, etc. Yet they are sumcientlystable to allow application from aqueous baths. Hence,,these newcompounds are of value for fixation of sizes, plasticization ofcellulose, waterproofing of fabrics, and similar applications. g

The quarternary ammonium compounds of the .above formula are prepared byreacting a disubacyl portion of their molecule such groups as aryl,

alkoxy, halogeno-, keto-, etc.

The secondary amine is one in which the nitrogen'is not linked-directlyto a phenyl or other aromatic group, but to an aliphatic or alicyclicgroup as in dimethylamine, diethylamine, diisopropylamine,methylpropylamine, diallylamine, morpholine, piperidine, methylcyclohexylamine, methyl benzylamine, etc. The lower aliphatic amines (i.e. those having not more than eight carbon atoms) are preferred, butother strongly basic secondary amines are likewisev useful, particularlythose in which R2 and R together form a divalent, saturated group whichwith the nitrogen yields a heterocycle.

The halomethyl ether may be prepared according to the method shown in U.8.. Patent No. 2,084,125 in which a primary or secondary aloctadecenyl,cetyl, octadecyl, benzyl, etc. alcohol or an alicyclic alcohol, such ascyclohexanol, and anhydrous formaldehyde, usually as paraformaldehyde,are reacted in a solvent with dry hydrogen chloride or bromide. Theseethers are very unstable toward water, yet it has been found that theymay be reacted with the aminomethyl amides to giverelatively stablequaternary ammonium salts.

The halomethyl ether and .the'aminomethyl amide are reacted merely bymixing the two materials. The reaction is generally spontaneous.

It is sometimes desirable to cool the reaction mixture to prevent toohigh temperatures. It is also sometimes advisable to warm the reactionmixture to complete the reaction. The reaction may, if desired,-becarried out in a-dry, inert solvent, such as benzene or toluene. Theresulting quaternary ammonium compounds are, in general, soluble inwater, unless both the chain from the amide and that from the etherarelong.

The preparation of the new compounds is illustrated by the followingexamples.

Erramplei 1 c1 onnuoonncmi romoozm V Hi):

During a minuteperlod 95 parts of ethyl chloromethyl ether was addedwith stirring to cohol, such as ethyl, isopropyl, n-butyl, isobutyl,

amyl, allyl, methallyl, undecenyl, dodecyl, 9, lQ-i maintained at C. Astiif paste dissolved in water to form a viscous solution.

450 parts of dirnethylaminomethyl stearamide resulted which Example z01111550 oNncmi rcmo 04H During the course of 30 minutes parts of nbutylchloromethyl ether was added with stirring to 450 parts of dimethylaminomethyl stearamide maintained at 55 C. A stiff paste resulted whichformed a viscous solution in water.

Example V I p o1 sumo0N1:crni romocim (CHs):

While the temperature was maintained at 40- 50 C., 18 parts of butylchloromethyl ether was added with stirring to 56 parts ofdimethylaminomethyl oleylamide. The mixture was stirred for one hourand-then cooled. It forms a thick paste which gave a soapy solution inwater.

Example 6 01 CizHz5OCONHCH2l ICHzOCHC H13 2 i CH: v

While the temperature was maintained between 40 50 C., 18 parts ofcapryl chloromethyl ether was added with stirring to parts ofN-diethylaminomethyl dodecyl carbamate. A waxy prod uct resulted whichformed a soapy solution in water.

The compounds having a chain of 12 or more carbon atoms, as shown, forexample, in Examples 1 and 4 above, are particularly effective for thewaterproofing of fabric. They are eifective on cotton, linen,regenerated cellulose, jute,

straw, silk, wool, etc., which may be impregnated with a solutioncontaining such a compound, dried, and then heated. A temperature as lowas 90 C. is efiective. At the low temperatures at which the abovecompounds become effective there is no damage to even the most delicatefibers 0r fabrics. ypical applications in waterproofing are shown in thefollowing examples.

(A) Cotton sheeting was dipped in a 3% solution of the compound obtainedin Example 1 above. The material was dried in a current of air at about40 C. and then placed in an oven at 110 C. for minutes. The cloth'wasvery water-repellent and this property was enhanced by rinsing in hotwater. Laundering did not remove the water-repellent property.

(B) A spun viscose rayon fabric was dipped in a warm 5% solution of thecompound prepared in Example No. 2 It was dried at room temperature andthen heated 10 minutes at 135 C. in an oven. Good water-repellency wasobtained.

(C) Cotton sheeting was dipped in a 5% solution of the compound preparedin'Example No.

4. It was baked in an oven at 120 C. for 30 minutes. The resultingmaterial was very waterrepellent, even after laundering.

The long-chained compounds are also useful as softening agents and maybe so used without heating or, if desired, fabric softened therewith ma:be heated to make this effect permanent.

Another use for the compounds is in the fixation of hydroxyl-containingsizes such as starch,

cellulose ethers, and polyvinyl alcohol. These materials readily reactwith any of the above quaternary compounds and for sized fabrics, wherea certain amount of crispness is desired, the short-chained derivatives,such as butyramidomethyl caproxymethyl dimethyl ammonium chloride, areof particular interest. If a long chain is present, there is softeningas well as insolubilizing of the size. The new dimethylene quaternaryammonium compounds are particularly efiective because both the acylgroup and the other group react.

Long-chained quaternary compounds of this invention are further usefulas wetting, emulsifying, and dispersing agents.

I claim:

1. The process of preparing a compound of the formula wherein R and R1represent aliphatic groups,

X represents a halogen, and R2 and Rs represent a member of the groupconsisting of lower aliphatic groups and divalent saturated groups whichjointly with the nitrogen form a heterocycle, which comprises mixing atertiary aminomethyl amide and a halomethyl ether of an alcohol selectedfrom a member of the group consisting of primary and secondary alcohols.

2. A'compound of the formula "wherein R and R1 represent aliphaticgroups, X represents a halogen, and R2 and R3 represent a member of thegroup consisting of lower aliphatic groups and divalent saturated'groupswhich jointly with the nitrogen form a heterocycle.

3. A compound of the formula C X CH:

wherein R and R1 represent aliphatic groups and X represents a halogen-I '4. A compound of the formula wherein R and R1 are aliphatichydrocarbon groups, oneof which contains at least twelve carbon atomsand X representsa halogen.

5. Stearamidomethyl ethoxymethyl dimethyl ammonium chloride.

6. Stearamidomethyl butoxymethyl dimethyl ammonium chloride.

7. Butyramidomethyl caproxymethyl dimethyl ammonium'chloride. 1

LOUIS H. BOOK.

